Boosting the ORR/OER Activity of Cobalt‐Based Nano‐Catalysts by Co 3d Orbital Regulation

Abstract The transition metal oxides/sulfides are considered promising catalysts due to their abundant resources, facile synthesis, and reasonable electrocatalytic activity. Herein, a significantly improved intrinsic catalytic activity is achieved for constructing a Co‐based nanocrystal (Co‐S@NC) with the coordination of Co─S, Co─S─C, and Co─N x ─C. The calculational and experimental results demonstrate that the diversified chemical environment of Co‐cations induces the transition of 3d orbitals to a high spin‐state that exhibits the coexistence of Co 2+ with fully occupied d π orbitals and Co 3+ with unpaired electrons in d π orbitals. The diverse d π orbitals occupation contributes to an elevated d‐band center of Co ions, which accelerates oxygen reduction reaction and oxygen evolution reaction electrocatalytic kinetics of the Co‐S@NC nanocrystal. Therefore, the Li–O 2 batteries with Co‐S@NC as cathode catalyst exhibit 300 cycles at the current density of 500 mA g −1 with a cut‐off capacity of 1000 mAh g −1 . Moreover, the ultrahigh discharge specific capacity of 34 587 mAh g −1 is obtained at a current density of 1000 mA g −1 , corresponding to the energy density 949 Wh kg −1 of a prototype Li–O 2 battery. The study on 3d orbital regulation of nanocrystals provides an innovative strategy for bifunctional electrocatalysts toward the practical application of metal–air batteries.